Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
  • C08G75/02—Polythioethers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
  • C08G75/02—Polythioethers
  • C08G75/0204—Polyarylenethioethers
  • C08G75/0286—Chemical after-treatment
  • C08G75/0295—Modification with inorganic compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
  • C08G75/18—Polysulfoxides

Definitions

• the invention relates to a process for the preparation of polyarylene sulfoxide by Oxidation of polyarylene sulfide.
• Polyarylene sulfoxides are technical specialty polymers, especially there Find application where high demands are placed on the polymeric material become.
• polyarylene sulfoxides are characterized by high glass, Melting and decomposition temperatures.
• Polyarylene sulfoxides are also technically interesting because they are used as high-temperature blowing agents for manufacturing of plastic foams.
• a known process for the production of polyphenylene sulfoxide (PPSO) is Conversion of low molecular weight slurried in acetic anhydride Polyphenylene sulfide (PPS) with 70% nitric acid (DE-A-1211399 / US-332686). Here, the reaction over a long period of 24 hours at one Temperature between 0 and 5 ° C carried out.
• PPSO polyphenylene sulfoxide
• DE-A-1938806 discloses a method in which polyarylene sulfide containing sulfonyl groups is oxidized in a sulfuric acid medium with oxygen or an oxygen-transferring agent, for example hydrogen peroxide (H 2 O 2 ).
• oxygen or an oxygen-transferring agent for example hydrogen peroxide (H 2 O 2 ).
• GB-1365486 also describes the oxidation of sulfonyl-containing polyarylene sulfide described.
• the polyarylene sulfide sulfone is dissolved in sulfuric acid and oxidized by adding a mixture of hydrogen peroxide and sulfuric acid.
• the sulfide units of the polyarylene sulfide sulfone are indeed partly also converted into sulfoxide units, but mostly takes place Conversion to sulfone units.
• EP-A-0791027 discloses a process for the oxidation of polyarylene thiothern with the equilibrium system NO 2 / N 2 O 4 , which leads to the formation of sulfoxide units with high selectivity, but, as recent studies have shown, nitro groups are sometimes incorporated onto the aromatic system.
• the object of the invention was to provide an economical method for Production of polyarylene sulfoxides to find the disadvantages of the known Processes, especially long reaction times and low selectivity, are overcome.
• polyarylene sulfides are linear or branched polymers which contain arylene sulfide units.
• Preferred polyarylene sulfides are polyarylene thioethers with repeating units of the formula - [(Ar 1 ) n -X] m - [(Ar 2 ) i -Y] j - [(Ar 3 ) k -Z] l - [(Ar 4 ) o -W] p - wherein Ar 1 , Ar 2 , Ar 3 , Ar 4 or W, X, Y and Z are independently the same or different, the indices n, m, i, j, k, l, o and p independently of one another zero or whole Numbers 1, 2, 3 or 4 are, their sum being at least 2, Ar 1 , Ar 2 , Ar 3 and Ar 4 are arylene systems with 6 to 18 C atoms and W, X, Y and Z represent divalent linking groups from
• the arylene systems Ar 1 , Ar 2 , Ar 3 and Ar 4 can be optionally substituted or unsubstituted.
• Preferred arylene systems are phenylene, biphenylene, naphthylene, anthracene and phenanthrene.
• a particularly preferred polyarylene sulfide is polyphenylene sulfide, which is known, inter alia, under the names ®Fortron and ®Ryton.
• a 30 to 100% hydrogen peroxide solution is generally metered into the polyarylene sulfide suspension as the oxidizing agent.
• concentration of the hydrogen peroxide solution is preferably 35 to 85%, particularly preferably 50 to 85%.
• the oxidation can also be carried out using a mixture of (A) 50 to 100% hydrogen peroxide solution and (B) 95 to 100% solution of an acid of the formula R-SO 3 H or of the formula R 1 -CR 2 R 3 - COOH take place, where R, R 1 , R 2 and R 3 are each one of the substituents defined above and the ratio A: B is from 10: 1 to 1:10.
• peroxosulphuric acid also called Caro's acid, which is prepared from concentrated hydrogen peroxide solution and concentrated sulfuric acid, or dichloroperacetic acid.
• the metered in Oxidizing agents distributed as quickly and well as possible in the polyarylene sulfide suspension and that the metering in at a temperature of -20 to +45 ° C, preferred at 0 to +25 ° C and particularly preferably at 5 to 20 ° C.
• the good and rapid distribution of the oxidizing agent is generally characterized by a strong one Mixing of the reaction mixture causes. This can be done by general known methods take place, for example by using powerful stirrers and baffles etc.
• it is advantageous to both the oxidizing agent also to cool the polyarylene sulfide suspension and the reaction mixture. In particular during the metering in of the oxidizing agent, care must be taken that the temperature does not rise too high, especially not above 45 ° C.
• the oxidizing agent should be added in such a way that from 0.1 to 2 mol equivalent Oxidizing agent is metered in per hour, with one molar equivalent of Amount of oxidizing agent used to oxidize one mole of sulfide units is needed.
• the metering is preferably 0.25 to 1 mol equivalent per Hour, particularly preferably 0.5 to 0.7 mol equivalent per hour.
• the molar amount of the oxidizing agent reacted should be approximately that molar amount of sulfide units in the polyarylene sulfide, i.e. the Ratio of the molar amount of oxidizing agent to the molar amount of sulfide units should be at most 1.05: 1 when adding the oxidizing agent in excess and Addition in the deficit should be a minimum of 0.98: 1.
• the reaction mixture is still 0.5 to 5 hours, preferably further 0.5 to 3 hours and particularly preferably 1 to 2 hours mixed to complete oxidation of the sulfide units to reach.
• the temperature is generally in the specified range held.
• the reaction mixture is preferably kept constant by cooling Temperature maintained.
• the reaction mixture can be diluted with water or ice water and filtered off, the polyarylene sulfoxide remaining in the filter and as a filtrate dilute acid is produced.
• this dilute acid for example from a previous approach, used for dilution become.
• the grain size of the product obtained can be influenced usually with better mixing and lower viscosity of the batch a smaller grain size is obtained. Grain sizes usually become smaller 70 ⁇ m is achieved, preferably less than or equal to 50 ⁇ m.
• the grain size of the polyarylene sulfide is generally 1 to 100 microns, preferably 5 to 75 microns and particularly preferably 5 to 45 microns.
• more than 90%, preferably more than 95% of the sulfide units are oxidized to sulfoxide units and usually less than 10%, preferably less than 5% to sulfone units. Of the proportion of remaining sulfide units is generally less than 5%, preferred less than 2%.
• the characteristic decomposition level of the according to the invention Process obtained polyarylene sulfoxide is usually compared to Products obtained by oxidation in nitric acid at 20 to 25 ° C higher Temperature.
• the Decomposition level determined by means of thermogravimetric analysis (TGA) Heating in air up to 500 ° C at 10 K / min, usually at 365 to 367 ° C, while PPS oxidized in nitric acid undergoes a decomposition step at 340 ° C having.
• TGA thermogravimetric analysis
• DSC differential scanning calorimetry
• the polyarylene sulfoxides produced by the process according to the invention can, depending on their respective glass or melting temperature, thermoplastic, by melt-pressing processes or by sintering processes are processed.
• thermoplastic processing molding compounds are made Polyarylene sulfoxide by common methods for thermoplastics such as injection molding and Extrusion converted into molded and functional parts. These molding compounds can also powdery fillers such as chalk, talc, clay and mica, fibrous Reinforcing agents such as glass, carbon, metal or polymer fibers, whiskers as well as usual additives and processing aids such as antioxidants, Contain lubricants, release agents and UV stabilizers.
• thermoplastically processable polyarylene sulfoxide are particularly popular as highly stressable functional components, for example in aircraft or Automotive and chemical apparatus engineering, use.
• Sintered parts made from polyarylene sulfoxide are mainly found there Use where high temperature and chemical resistance is required.
• Polyarylene sulfoxides can also be used as fillers and reinforcing materials or as Use high temperature chemical blowing agent for other polymers.

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Inorganic Chemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)

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• 1997
  • 1997-11-19 DE DE19751239A patent/DE19751239A1/de not_active Withdrawn
• 1998
  • 1998-11-17 EP EP98121823A patent/EP0918063B1/fr not_active Expired - Lifetime
  • 1998-11-17 DE DE59804189T patent/DE59804189D1/de not_active Expired - Fee Related
  • 1998-11-19 JP JP10329180A patent/JPH11228696A/ja active Pending
  • 1998-11-19 US US09/195,402 patent/US6013761A/en not_active Expired - Fee Related
  • 1998-11-19 KR KR1019980049659A patent/KR19990045399A/ko not_active Application Discontinuation

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